Catalysts for production of 1-naphthol



United States Patent Ofilice 3,354,231 Patented Nov. 21, 1&6?

3,354,231 CATALYfrTS FOR PRODUCTION OF l-NAPHTHGL Arthur L. Maioy, SouthCharleston, and Robert W. Cunningham, St. Albans, W. Va., assignors toUnion Carbide Corporation, a corporation of New York No Drawing. FiledSept. 11, 1963, Ser. No. 308,092 4 Claims. (Cl. 260621) This inventionrelates to improved nickel-containing catalyst compositions. Moreparticularly, this invention relates to improved nickel-containingcatalysts having utility in hydrogenation and dehydrogenation reactions.In another, and still more particular aspect, this invention relates toimproved nickel-containing catalysts for the dehydrogenation of mixturesof l,2,3,4-tetrahydro-l-naphthol and 1,2,3,4-tetrahydronaphthalene-l-oneto l-naphthol.

In U.S. Patent 2,588,359, there are disclosed nickel catalysts havingparticular utility in hydrogenation and dehydrogenation reactions. Thesecatalysts, .in addition to nickel, contain, based on the weight of thenickel, from 15 to 40 weight percent copper, from 0.5 to 4 Weightpercent chromium in the form of an oxide, and from 0.3 up to 2.0 Weightpercent of one or more alkali metal sulfates. It was believed that allthese constituents were essential to the efficient operation of thehydrogenation or dehydrogenation process, More recently it wasdiscovered that the stability of these catalysts could be increased byincreasing the sulfur content of the catalyst so that the alkali metalswere present in the form of their sulfates or pyrosulfates.

Although these catalysts were generally satisfactory, it was found that,when reactivated, they were often less efficient as catalysts and, insome instances, had very little catalytic activity. It has beenunexpectedly and surprisingly found by this invention, however, that ifthe copper is not present in the catalyst it is readily reactivated and,after reactivation, may have improved efficiencies over the initialcatalysts. In addition, the catalyst of this invention is capable ofcatalyzing reactions at higher feed rates with no loss in yield,conversion or eliiciency when compared With the copper-containingcatalysts.

The catalysts of this invention consist essentially of nickel and, basedon the Weight of the nickel, from 0.5 to 4 percent chromium, mostly inthe form of its oxide; from 1 to 3 Weight percent of an alkali metalselected from the group consisting of sodium or potassium or mixturesthereof, a portion of said alkali metal being in the form of itssulfate; and sulfur in a molar ratio of said alkali metal to sulfur offrom 1.2 to 8, said sulfur being in the form of a sulfate of said alkalimetal. When the molar ratio of alkali metal to sulfur is at least 2, thesulfur Will be in the form of an alkali metal sulfate. When this ratiois less than 2, the sulfur will be present in the form of an alkalimetal sulfate and/ or an alkali metal pyrosulfate.

In addition, platinum metals such as platinum or palladium, which arecommonly employed as promoters for nickel catalysts, can be present ifdesired, but are not necessary.

It is essential, however, that the catalyst contain substantially nocopper, i.e., that the copper content of the caalyst be less than 0.1weight percent, based on the Weight of the nickel.

The preferred catalyst consists of nickel and, based on the weight ofthe nickel, from 1 to 2 Weight percent chromium, mostly, in the form ofits oxide, from 1 to 3 Weight percent sodium, a portion of which is inthe form of its sulfate salt, from 0 to 0.4 weight percent of potassium,a portion of which is in the form of its sulfate salt, and sulfur in theform of an alkali metal sulfate, wherein the molar ratio of the alkalimetal to the sulfur is from 2 to 4.

The catalysts are employed in the form of a support material impregnatedwith the catalyst components in the desired ratio. The catalyst supportcan be any material which is inert, both chemically and catalytically,is porous and which possesses a reasonable degree of physical strength,such as ceramically bonded silica, alumina and the like. Some of thecommercially available support materials contain small amounts of alkalimetal, particularly potassium. In such cases the amount of the alkalimetal in the support material should be included in determining theproportions of the catalyst components.

The catalysts are prepared by impregnating the support material with themetals in the desired proportions. This is conveniently effected byimmersing the support material in an aqueous solution of water solublesalts of the metals in suitable proportions. The salts should besubstantially free of sulfur compounds such as mercaptans and sulfidesor unknown contaminants, which may adversely affect the activity of thecatalyst product. Pure nickel is obtained by dissolving slabelectrolytic nickel in nitric acid to produce the corresponding nitrate.Chromium is conveniently obtained as chromium acetate. The alkali metalscan be added as sulfates or nitrates. If nitrates are employed, sulfuricacid should be added to the aqueous solution to convert the nitrates tosulfates.

After impregnation of the support material with the aqueous solution,the resulting mixture is evaporated to dryness and then roasted at atemperature of about 375 to 400 C. for a period of time sufiicient todecompose the nitrates, as determined by the cessation of the evolutionof nitrogen oxides. The impregnation and roasting can be repeated one ormore times as desired. In general, it is preferred that the catalystcontain from about 6 to about 18, preferably from about 12 to about 14,weight percent nickel based on the Weight of the entire catalyst.

After the final roasting to drive off the nitrogen oxides the catalystis activated by an oxidation-reduction cycle, wherein the catalyst isoxidized by heating in air at about 375 C. for about 2 hours; and thenreduced by heating at about 375 C. in a hydrogen atmosphere for up toabout 8 hours or more. This cycle can be repeated one or more times asdesired.

The following examples are illustrative of this invention. Thedehydrogenation processes shown in the examples illustrate the use ofthe catalyst of this invention in a two-stage conversion of a mixture ofl,2,3,4-tetrahydronaphthalene-Lone and 1,2,3,4-tetrahydro-l-naphthol tol-naphthol. In this process, the first stage is conducted under mildconditions wherein the 1,2,3,4-tetrahydro-1- naphthol is converted to1,2,3,4-tetrahydronaphthalene-lone and the yield of l-naphthol is notmaximized, and the second stage is conducted at higher temperatures toconvert the 1,2,3,4-tetrahydronaphthalene-l-one to l-naphthol. Thissequence has been found necessary to the ethcient operation of thedehydrogenation, for if the initial 1,2,3,4-tetrahydronaphthalene-l-one1,2,3,4 tetrahydrol-naphthol mixture is dehydrogenated at temperaturessufficient to produce a maximum yield of l-naphthol, the1,2,3,4-tetrahydro-l-naphthol, instead of dehydrogenating to1,2,3,4-tetrahydronaphthalene-1-one, dehydrates to formdihydronaphthalene. In the examples the yield, concomposition for eachof the three runs, the duration of version and etliciencies weredetermined by the following each run, the yield of l-naphthol, and theefliciency and equations: degree of conversion of the reaction, based onthe l,2,3,4-

Percent l-naphthol out l-naphthol in y1,2,3,4-tetrahydronaphthalene-l-one 1,2,3,4-tetrahy dro-l-uaphthol in:IXIOO(1,2,3,4-tetrahyclronaphthalene-l-one+1,2,3,4-tetrahydro-l-naphtholout.) Pelcent conversloni:1,2,3,4-tetrahydronaphthalene-l-one+1,2,3,4-tetrahydr-l-naphthol in4-tetrahydronaphthalene-l-one 1,2,3,4-tetrahydro-1-naphthol in) -:l

Percent efficiency naphthol out naphthol in :l 1001,2,3,4-tetrahydro-1-11aphthol+ l,2,3,4-tetrahydronaphthalene-l-one in),2,3,4-tetrahydro-l-naphthol 1,2,3,4-tetrahydronaphthalene-l-one out)Example 1 tetrahydro-l-naphthol and 1,2,3,4-tetrahydronaphthalene- Onchundred forty grams of powderad nickel were l-one in the feed aresummarized in tabular form below:

solved in a stoichiometric excess of 70 percent nitric acid.

The solution was heated to boiling and 1.30 grams of an Run aqueoussolution of chromium acetate (20 weight per- Feed Composition centcalculated as Cr O 10.4 grams of sodium nitrate 1 2 3 dissolved inwater, and 5 grams of concentrated sulfuric acid were added. Aboutone-third of the resulting solution 1,2,3,ammilydwnwmhaienal.one, wt wasthoroughly admixed with 847 grams of 2 X 4 mesh cent 1- Y, A I 1l-uaphthol, wt. percent 10.0 31.5 39.3 AlOkliB. (CfllbOlUl'lClllIllbrand, porous, ceram l Y 1,2,15,4-tetrahydrol-uaphthol, wt. percent...3.4 1.7 5.2 bonded alumina pellets containing small amounts ofNaphthalene P h 1 Dmydronaphthalene, wt. percei 1.0 0.8 0. 8 p u) 111ml6 Sohds appeared to be y y V1511? '1etrahydronaphthalene,\vt.pe1 1.4 5.52.3 observation. The impregnated pellets were then heated lo 40 gggigkf'fifig 2 Q afofced-air o ven at 75-380 0. for12 hours. Enploy ngssei t re csaay. ::::::::::::::::::::::::::i at 7 sirni '11 roce ures te rema'ninso tion was e osite "1111111 101 c p l h 0 u d n ierceut yield(average) 81.3 83.9 84.3 1n tWO equa portions On t e impre nate pe etS.Percent elhciency (average). 95.7 98.7 98. 6 The impregnated pelletswere then charged to a 1.5 lerwltconvel'swn(average 8 -8 85-1 8 x60-inch stainless steel, Dowtherm-heated converter and heated to 375 :2C. Air was passed through the catalyst for 2 hours at a rate of 16liters of air per hour to oxidize Example 3 the metals present. Thesystem was then purged of air with nitrogen and the catalyst was reducedby passing hydrogen at a rate of 16 liters per hour through the catalystfor 2 hours, followed by a second nitrogen purge. Theoxidation-reduction cycle was repeated, except that the oxidation wasconducted for 6 hours and the reduction was conducted for 14 hours. Theresulting catalyst contained 14.08 Weight percent nickel in the form ofits metal, 0.175 Weight percent chromium (1.24 percent based on nickel),mostly in the form of its oxide, 0.027

In a manner similar to that described in Example 2, except that thecatalyst contained 13 weight percent nickel, 0.225 weight percentchromium (1.73 percent based on nickel), 0.034 weight percent potassium(0.26 percent based on nickel), 0.27 weight percent sodium (2.08 percentbased on nickel), and 0.405 percent sulfate (3.11 percent based onnickel), a feed identical to that employed in run 1 of Example 2 wasdehydrogenated to produce l-naphthol. The conditions employed were asweight percent potassium (0.19 percent based on nickel) follows: partlyin the form of its sulfate, 0.29 weight percent catalystbed temperatum oC 375 sodium (2.06 percent based on nickel) partly in the form pressure,Psi" 7 7 n 10 of its sulfate, and 0.445 percent of sulfate (3.16 percentFeed rate, mL/i/hn 73 based on nickel), in the form of an alkali metalsulfate. Hydrogen to feed mole ratio 55:1

Example 2 The results are summarized in tabular form below:

The catalyst produced as described in Example 1 was employed todehydrogenate 1,2,3,4-tetrahydronaphthalene-l-one to l-naphthol. Theconditions for the reaction 1 2 3 were 375 C. catalyst bed temperature,10 p.s.i.g. pres- U sure, 278 milliliters of feed per liter of catalystvolume 508 3 i per hour and a 5.6 to 1 mole ratio of hydrogen to feed.l-uaphthol: m The catalyst was reactivated twice during this experimentg'g 23 -3 by employing procedures similar to those described inConversion 84:6 84:5

Example 1 for the initial catalyst activation. The feed riment bed forWhile C. After going expe ir through the ining a maximum catalysttempera- C., and then passing hydrogen at a rate of hour through the bedfor 19 hours -1-one 1,2,3,4-tetrahydropassed through the bed. The intabular form below:

The catalyst employed in the fore was then reactivated by passing a 54hours While mainta ture of 425 16 liters per maintaining a maximum bedtemperature of 383 reactivation, the bed was maintained at 290 C. andthe 1,2,3,4-tetrahydronaphthalene l-naphthol feed was again resultsofthis run are summarized Example 4 Employing the catalyst described inExample 3, a feed consisting of 63.8 weight percent 1,2,3,4tetrahydronaphthalene-l-one, 32.7 weight percent 1,2,3,4tetrahydro-1-naphthol and 0.5 weight percent tetrahydronaphthalene was dehydrogenatedunder conditions sufficient to convert the 1,2,3,4-tetrahydro-1-naphth01to 1,2,3,4-tetrahydronnphthalene-l-one without under formation of hyeemafl m n r m m y mwnmnwwwwe to k n a m nn du n n 86 311548523 3 h I a 0Com m 2 3 4 4a4 5 5 5 m e 0d 6 m H 9888888 8 8 d C 6 d mm P rps d w E Eaaa t flflVn 1 mo .l a mlu. n 2861641396 3 S yu m e P among men a H S tPP HS .2 manwwew ma .1 mm 117323299 9 w m N W C mm t 0 a mmenuuewn u amn m 0 PO 5 Aw tu we C k r3 W nm D. e d 4470039605 4 l m m m P a 33333 am m bcfi m Y t t E S wfiw n nd U h 6 w 1 240437962 2 1 M tA e W I mm 6 20 7 7da4 & & al Y m m H DBHY 444333333 3 M p m 0 1 W um mm H 818716687.s n U Mm Omo7 5 5 6 356 6 6 g mov mm .mm ,cnla mm mt. y 3n r. n d2isid d0 16 .lte y, mm 581835411 1 p h nn H mm &7 7 5&&6 6 6 6 m n m m t mm.Mt. E W n m m m d 8637066343 7 y O Hu hht 6 HO n 2544545667 4 H d WSC ww wn 5 nD 4 4 m 04 t 3M5... 1 S 1 minno a W16: m mm 4mm en nee 4 3 a MWW 111121111 1 4 w m 0502418758 3 ayt h a 0 w r m g mnemuonwmw e a 1 d lh m u C 1P ww wm. M w u u n a 3.0 t H 1". t m. m .mh w m e n o 1 tam w mf wm nw 342709830 1 e u n n u m. 2 68795250 v w mo m m n u m ma mmwwwfium w m .w n u w mm n .H n u t WP m u u .m mt .O C d 1w a m 0 o n B F he a.1 0000000000 mm 1336 .6 m m n .m m m m we nnmwmwwam m a w a. nt 3 a .OMC 1W r. m H e I 6 S m u e P 6 6 h m .16 r T n ego/.e a q H T mi m s u St. mm m e e u. .t w in n m. a nun b wn w 0w ma 1 3 r. t S a e m w a N wsN a s M 10 A 3W w law h mp 9 CO S d O 8 o e T 3 m Id re 2 1 df W *Feedchanged to 59.0 percent 1,2,3,4-tetrahydronaphthalene-l-one, 38.0 weightpercent l,2,3,4-tetrahydro-l-naphthol and 1.3 weight percenttetrahydronaphthalene after 629 hours of operation,

7 nickel. The results and operating conditions for these two runs areset forth in tabular form below:

Run

Catalysts-Component, wt. percent based on tan- From the above data it isclear that the copperless catalyst of this invention is superior to asimilar catalyst containing copper. At a feed rate over 45 percent inexcess of the rate employed with the copper-containing catalyst thecatalyst of this invention permitted a 144 percent increase in yield ofl-naphtbol, a 77 percent increase in conversion of1,2,3,4-tetrahydro-1-naphthol and 1,2,3,- 4-tetrahydronaphthalene-I-oneto naphthol and a 38 per cent increase in etficiency of the process.

In addition, it has been found that, in the first stage of thedehydrogenation process, when the copper-containing catalyst isemployed, the conversion of 1,2,3,4-tetrahydrol-naphthol and1,2,3,4-tetrahydronaphthalene-1-one to l-naphthol decreases whenconditions are maintained to limit the dehydration of1,2,3,4-tetrahydro-l-naphthol to dihydronaphthalene to less than 10percent of the 1,2,3,4- tetrahydro-l-naphthol. On the other band, thedegree of conversion increases while maintaining the1,2,3,4-tetrahydro-l-naphthol loss to less than 7 percent, thusincreasing the overall yield of naphthol and the efficiency of theentire system.

What is claimed is:

1. A catalyst consisting essentially of an admixture of nickel and,based on the weight of said nickel, from 0.5 to 4 weight percentchromium, substantially in the form of its oxide, from 1 to 3 weightpercent of an alkali metal selected from the group consisting of sodium,potassium and mixtures thereof, a portion of said alkali metal being inthe form of a sulfate of said alkali metal, the'sulfur of said sulfatebeing present in a ratio from 1.2 to 8 based on the mole ratio of saidalkali metal to said sulfur.

2. A catalyst consisting essentially of an admixture of nickel and,based on the weight of said nickel, from 1 to 2 weight percent chromium,substantially in the form of its oxide, from 1 to 3 Weight percentsodium, a portion of which is in the form of its sulfate, from 0 to 0.4Weight percent potassium, a portion of which is in the form of itssulfate salt, the sulfur of said sulfate being present in a ratio from 2to 4 based on the mole ratio of said sodium and said potassium to saidsulfur.

3. In a process for the catalytic dehydrogenation of a member selectedfrom the group consisting of 1,2,3,4- tetrahydronaphthalene-l-one,1,2,3,4-tetrahydro-l-naphthol, and mixtures thereof to form l-naphthol,the improvement of conducting said dehydrogenation in contact with acatalyst consisting essentially of an admixture of nickel and, based onthe weight of said nickel, from 0.5 to 4 percent chromium, substantiallyin the form of its oxide, from 1 to 3 weight percent of an alkali metalselected from the group consisting of sodium, potassium and mixturesthereof, a portion of said alkali metal being in the form of a sulfateof said alkali metal, the sulfur of said sulfate being present in aratio from 1.2 to 8 based on the mole ratio of said alkali metal to saidsulfur.

4. In a process for the catalytic dehydrogenation of a member selectedfrom the group consisting of '1,2,3,4- tetrahydronaphth alenel-one,1,2,3 ,4-tetrahydrol-naph- 'thol, and mixtures thereof to form'l-naphthol, the improvement of conducting said dehydrogenation incontact with a catalyst consisting essentially of an admixture ofnickel, and based on the weight of said nickel, from 1 to 2 weightpercent chromium substantially in the form of its oxide, from 1 to 3weight percent sodium a portion of which is in the form of its sulfate,from 0 to 0.04 weight percent potassium, a portion of which is in theform of its sulfate salt, the sulfur of said sulfate being present in aratio of 2 to 4 based on the mole ratio of said sodium and saidpotassium to said sulfur.

References Cited UNITED STATES PATENTS 3/1952 Chitwood et a1. 260621 X1/1964 Royce 25t2470 X

1. A CATALYST CONSISTING ESSENTIALLY OF AN ADMIXTURE OF NICKEL AND,BASED ONTHE WEIGHT OF SAID NICKEL, FROM 0.5 TO 4 WEIGHT PERCENTCHROMIUM, SUBSTANTIALLY IN THE FORM OF ITS OXIDE, FROM 1 TO 3 WEIGHTPERCENT OF AN ALKALI METAL SELECTED FROM THE GROUP CONSISTING OF SODIUM,POTASSIUM AND MIXTURES THEREOF, A PORTION OF SAID ALKALI METAL BEING INTHE FORMOF A SULFATE OF SAID ALKALI METAL, THE SULFUR OF SAID SULFATEBEING PRESENT IN A RATIO FROM 1.2 TO 8 BASED ON THE MOLE RATIO OF SAIDALKALI METAL TO SAID SULFUR.
 3. IN A PROCESS FOR THE CATALYTICDEHYDROGENATION OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF1,2,3,4TETRAHYDRONAPHTHALENE-1-ONE, 1,2,3,4-TETRAHYDRO-1-NAPHTHOL, ANDMIXTURES THEREOF TO FORM 1-NAPHTHOL, THE IMPROVEMENT OF CONDUCTING SAIDDEHYDROGENATION IN CONTACT WITH A CATALYST CONSISTING ESSENTIALLY OF ANADMIXTURE OF NICKEL AND, BASED ON THE WEIGHT OF SAID NICKEL, FROM 0.5 TO4 PERCENT CHROMIUM, SUBSTANTIALLY IN THE FORM OF ITS OXIDE, FROM 1 TO 3WEIGHT PERCENT OF AN ALKALI METAL SELECTED FROM THE GROUP CONSISTING OFSODIUM, POTASSIUM AND MIXTURES THEREOF, A PORTION OF SAID ALKALI METALBEING IN THE FORM OF A SULFATE OF SAID ALKALI METAL, THE SULFUR OF SAIDSULFATE BEING PRESENT IN A RATION FROM 1.2 TO 8 BASED ON THE MOLE RATIOOF SAID ALKALI METAL TO SAID SULFUR.